Abstract
Organic compounds based on ferrocene, pyrazolone, and octahydroacridine exhibit high interest due to their unusual structure, with potential practical applications due to their special optical properties. Nonlinear optical (NLO) properties of some new synthesized derivatives are evaluated in relationship with the chemical structure by using DFT molecular modeling. In condensed state, ferrocene and other organic molecules were found in a staggered arrangement (D5d) as a nonpolar molecule, but the eclipsed (D5h) and twisted (D5) forms exhibit SHG capabilities. The molecular polarizability (α), first-order hyperpolarizabilities (βtot), dipole (μtot), and quadrupole (Q) moments were computed. The NLO efficiency was assessed by the relationship between high (βtot) and low HOMO-LUMO energy gap. The nonlinear optical properties of some new synthesized compounds were evaluated in thin films with nanometric morphology obtained using various methods: Langmuir-Blodgett (LB) thin films, sol-gel deposition, and layer-by-layer deposition.
Keywords
- nonlinear optics
- thin films
- nanostructures
- hybrid materials
- Langmuir-Blodgett film
- layer by layer
1. Introduction
Nonlinear optics has become a vibrant field of research since the optical second-harmonic generation (SHG) was first observed in the early 1960s [1]. A better understanding was achieved on the origin of nonlinear optical (NLO) phenomena and the structure-property relationships of NLO chromophores in the late 1970s when various tools were developed to accurately measure and calculate hyperpolarizabilities [2]. Organic NLO materials, which can be modulated and processed readily, are of much contemporary interest because of their potential applications in modulation of optical signals, medicine, spectroscopic and electrochemical sensing, microfabrication and imaging, laser technology, data storage, and telecommunication [3]. Recent studies were focused on the synthesis of the organic molecules with special geometry and certain electronic molecular parameters to possess nonlinear optical (NLO) properties [3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24]. The demand of substances with NLO properties for numerous industrial applications has resulted in many articles reporting the manufacture of various novel molecules, with highly active chromophores and superior optical activity. However, it remains the issue of processing these materials, as long as the specific optical properties have to be preserved, together with new requirements added, such as chemical stability, mechanical strength, etc. The main materials used as host for the embedding of chromophores and fabrication methods are discussed. The influence of parameters (such as chemical structure of the host material, synthesis conditions, and external stimuli) on the optical and electrical properties of the final product is also evidenced.
2. Synthesis of compounds with NLO properties
Recent literature shows some classes of organic compounds suitable for applications for molecular switches that possess certain characteristics, such as high molecular hyperpolarizability coefficients (
2.1. Alkyne compounds
Ryhding et al. synthesized by Sonogashira Pd-catalyzed cross-coupling reactions a series of new oligo(
The new derivatives
2.2. Push-pull derivatives as NLO chromophores
The organic molecules which contain a couple, donor (D)-acceptor (A) (or “push-pull” system), connected to a system which contributes to the delocalization of the π-electrons make the
There are several classes of organic compounds in this category, from which some representatives will be presented.
2.2.1. Push-pull dyes
Arylazo-5-alkoxy-2,2′-bithiophene-conjugated dyes
Kleinpeter et al. demonstrated that compounds
2.2.2. Push-pull structures from different classes of heterocyclic compounds
Push-pull molecular structures based on angular benzobisthiazolium acceptor were synthesized by Cibova et al. A comparison of selected spectral and nonlinear optical properties of the prepared compounds shows that compound
The compounds
2.3. Thienyl compounds as NLO materials
Thiophenes are among the most studied heterocyclic spacers for D-π-A systems due to their relatively low resonance energies and have allowed the preparation of chromophores with high stabilities and nonlinearities [44]. Raposo et al. reported the synthesis of formyl-substituted 1-alkyl(aryl)-2-(2′-thienyl)pyrroles
2.4. Ferrocene derivatives
Ferrocene (
Yang et al. synthesized two electron-donating π-acceptor (D-π-A) chromospheres
Both compounds exhibited reverse saturable absorption (RSA) and optical limiting effect under nanosecond pulse irradiation. Matei et al. synthesized 4-(ferrocenylmethylimino)-2-hydroxy-benzoic
The synthesis of the dendrimers with vinyl ferrocene was carried out applying the convergent Frechet approach that consists of three steps: (1) the synthesis of the two conjugated dendrons, (2) the selective formation of resorcinarenes bearing three different solubilizing groups, and (3) the alkylation of the dendrons to the resorcinarenes. Under this order, dendrons containing ferrocenylvinyl groups were prepared starting from a Heck reaction coupling of 3,5-dibromo-benzaldehyde with vinyl ferrocene in dimethylformamide/triethylamine (1:0.25) using palladium acetate as catalyst. The χ(3) values estimated from the THG Maker fringe technique for ferrocenyl-ended resorcinarene dendrimers dispersed in thin solid films are of the order of 10−12 esu.
Villalonga-Barber et al. synthesized new dodecaferrocenyl dendrimer
3. Fabrication of thin films with NLO properties
For most practical uses, substances with NLO properties are incorporated into a host material to ensure good dispersibility and stability. Thus, in most of the cases, polymers are used, usually with electrical and optical properties to improve the performance of the hybrid system. The polymeric derivatives applicable as matrices are the ones with high thermal stability and optical transparency. A large variety of polymers were tested as host matrix, such as polymethyl methacrylates, polyether ketones, polyimides, and polycarbonates. The most used material is polymethyl methacrylate, due to its intrinsic optical properties, stability, functionalization possibilities, and processability. Another material used as the host for NLO substances is silica matrix, which has important advantages: the facility and flexibility of syntheses as well as the possibility of processing them as thin films. Ji et al. [64, 65] report the successful embedding of Disperse Red 1 as chromophore in a silica glass prepared by using sol-gel synthesis. The silicate precursor was a new derivative 1,4 phenylene bis(4-trimethoxysilyl ethyl benzoate), with a structure that allows uniform dispersion and accommodates the chromophore molecules in the cross-linked polymeric matrix (see Figure 8).
The hybrid film is fabricated by in situ poling and sol-gel synthesis. The final material exhibits an efficient NLO behavior, with a very good thermal stability (the SHG signal is stable until 120°C, and the half decay temperature is 170°C.
Another advantage of silica as host material is the possibility to prepare polymer-silica hybrid matrix that combines the best properties from both substances. An interpenetrating polymer-silica matrix was prepared [66] from polymerization of γ-methacrylpropyl)-silsesquioxane and an allyl glycidyl ether modified chromophore (Disperse Orange 3 (DO3)). The high degree of cross-link density and order leads to enhancement of the nonresonant second-order nonlinearity in the film obtained. Unfortunately, the process is very difficult and laborious, since the incorporation of the NLO chromophore in the polymer-silica network is a three-step synthesis: (i) functionalization of DO3 with glycidyl ether, (ii) synthesis of monomer (γ-methacrylpropyl)-silsesquioxane using hydrolytic condensation of commercially available silane derivative, and (iii) the preparation of NLO embedded matrix through the free radical polymerization of modified chromophore and methacrylpropyl compound and the simultaneous cross-linking of the network [66].
The AFM images of the DO3-doped methacrylate-silica film before and after poling demonstrate that the poling process allows a better orientational order of the chromophore molecules (see Figure 9).
This material exhibits a very good temporal stability of the chromophore orientation in the interpenetrated hybrid polymer-silica matrix, together with superior NLO properties.
Silica material mentioned above could also provide the sites to adjust covalent bonding of the chromophores. Recently, Laskowska et al. [67] reported the fabrication of NLO thin films from a novel functionalized mesoporous silica material as host matrix. To show the efficiency of the concept in tuning the NLO behavior from the morphology of the silica matrix, a very simple optically active compound is proposed, a dipolar copper propyl phosphonate fragment. The copper-containing functional groups are covalently linked to the silica wall inside the pore of the matrix. The structure of the proposed material is presented schematically in Figure 10.
The host matrix consists in mesoporous silica thin films with 2D hexagonally distributed nanometric pores. The suitable morphological characteristics of the silica material, with hexagonal pores, regularly 2D distributed and aligned perpendicularly to the substrate, provide large specific area for easy access to the pore interior and lead to a high loading of the active chromophore. Moreover, the optical active moieties are very uniformly distributed.
Since the SHG signal obtained depends on the concentration of the NLO fragments, the material with tunable NLO response could be obtained by adjusting the functionalization degree from the synthesis parameters.
4. The arrangement of chromophores in polymeric host matrix
The macromolecular host matrix encapsulates the chromophores either dispersed or attached on the polymeric chain. In both cases, the most important issue that appears is the proper arrangement of NLO active molecules. The common procedure to obtain the required noncentrosymmetric arrangement for the dipolar push-pull chromophores embedded in a polymeric matrix is based on electric field poling process. It consists in the application of the electric field across the material, when heating the system to the glass transition temperature (Tg) of the polymer.
When photosensitive dyes are encapsulated, for example, azo-derivatives, light can be used in order to replace the heating procedure (photoassisted poling). This method is a choice when temperature-sensitive NLO molecules are involved, enabling poling process preformed at temperatures well below Tg. A large variety of azo-derivatives have been poled using this method (1).
Other guest molecules may be covalently bonded to the polymer chain, but the chemistry involved in the attachment of the chromophore to the macromolecule still remains a major challenge. Severe conditions in synthesis and processing employed to prepare most of side-chain NLO polymers (polymers with grafted chromophore as side chain) limit their practical application. The use of these polymer-based materials generates several film properties required for photonic applications, such as thermal and chemical stability, high loading of the active molecule, and stability of the chromophore orientation [68]. Highly cross-linking of side-chain polymers enhances the stability of the thin film together with the chromophore moiety arrangement.
Another covalent bonded variant is main-chain NLO polymer, with chromophores linked in the backbone at either end of the chromophore or linked at both ends of the chromophores, to form the polymer backbone. The dye fragment can be processed in various configurations: a head-to-tail (isoregic), head-to-head (syndioregic), or in random head-to-tail and head-to-head configurations (aregic) (2) [69].
4.1. Langmuir-Blodgett films
The most efficient way to obtain the arrangement of the large dye molecules is to take advantage from their intrinsic self-assembling ability. Hydrophobically modified chemicals that exhibit NLO properties can be efficiently organized as 2D structure using the Langmuir-Blodgett technique. Formation of the coherent and stable Langmuir film at liquid-air interface is mandatory for the further step, the transfer on solid substrate. The self-assembling properties of the NLO compounds could be tuned by chemical modification of the chromophore with various groups with suitable hydrophobicity, but the chemical modification will also influence the optical properties.
Tang et al. [70] report a study on the influence of the terminal group of the modified amphiphilic azobenzene chromophore on the Langmuir-Blodgett monolayer and multilayer formation. The azobenzene NLO derivative was modified with various electron acceptor groups (acetyl, nitro, and cyano), and the self-assembling behavior of the resulted compounds was investigated, to produce monolayers and multilayers deposited onto hydrophobically treated quartz substrate.
The experimental data confirm the molecular modeling conclusion that the packing of modified azobenzene molecules at the water-air interface and the transfer of the film are both due to the equilibrium of non-covalent interactions in the aggregates, dipol-dipol and π-π stacking interactions, respectively. The packing density and the electronic coupling vary strongly with the chemical structure of the functional group (see Figure 11).
The possibility to control the internal morphology and stability of the film through the balance of non-covalent interactions leads to the preparation of highly ordered multilayered film with large second-order susceptibility.
Most of the NLO chromophores could not be chemically modified to achieve suitable properties for spreading as Langmuir monolayers at the air-liquid or liquid-liquid interfaces; thus, the formation of Langmuir-Blodgett film is restricted to compound with a required degree of amphiphilicity. At the same time, many NLO materials processed by using Langmuir-Blodgett technique exhibit poor mechanical stability and limited surface area for deposition. A more sophisticated method to ensure the orientation of the chromophore molecules in the polymeric host network is to produce self-assembled thin film with the aid of film-forming matrix.
Usually, Langmuir-Blodgett films are obtained from Langmuir film deposited at the air-water interfaces with the well-known orientation of the molecule with the hydrophobic groups in air and hydrophilic ones immersed in water.
The driving forces of coherent monolayer formation are the hydrophobic interactions between the nonpolar parts and the interaction between the polar groups and the water subphase. Wang et al. [71] propose an unconventional method to prepare NLO LB films based on the molecular electrostatic interaction of hydrogen bonding in a chromophore modified with urea. The new synthesized optic active compound is 1-(10’-[(10-nitro)-6,7-azobenzenl]-ether-decyl)-3-(tetracosa-12,14-diynyl)urea (NAEDTDU), which exhibits an unusual packing behavior at air-water interface as it is proven by the П-A isotherm (see Figure 12).
The recorded specific molecular area of NAEDTDU is 35 Å2/molecule, smaller than the molecular area of the usual urea-containing derivatives in Langmuir film (50 Å2/molecule).
When assuming a traditional orientation of NAEDTDU molecule in the monolayer, with the urea polar group in the water subphase and both hydrophobic alkyl chain and nitro-azobenzene group in air, the molecular modeling suggests specific surface area larger than 50 Å2/molecule. To obtain the observed 35 Å2/molecule value, it is presumable that the nitro group of chromophore molecule lies on the air-water interface. Langmuir NAEDTDU monolayer can be transferred onto a hydrophobically modified quartz and silicon substrates using conventional vertical upward dipping technique and produces Langmuir-Blodgett multilayers. In this nontraditional LB monolayer, a peculiar aggregation of the chromophore molecules is suggested, i.e., the formation of a stable and linear network based on the hydrogen bonding between the urea groups.
The noncentrosymmetric arrangement of the NAEDTDU molecule in LB films generates relatively large intensities of SHG signal recorded. The thermal stability of SHG activity of LB multilayers was improved after photopolymerization of diacetylene moieties in film, due to the restriction of the movement of the chromophores and stabilization of their ordered orientation.
4.2. Layer-by-layer deposited thin films
The layer-by-layer (LbL) method to produce thin films is a versatile and convenient technique for the fabrication of thin films, based on the electrostatic attraction between the materials in different layers successively deposited. The most relevant advantage of LbL technique is represented by the precise control of the composition and thickness of the final film, which can be easily tuned from the chemical structure of the polyelectrolytes and deposition parameters. Acentric supramolecular architecture, as essential requirement for preservation of NLO properties, is a challenge to be achieved from chromophores and polyelectrolytes in LbL film technique. The conventional LbL technique should be adjusted in order to ensure the density and stability of the optic active molecules in the obtained film, with particular attention to be paid to the orientation of chromophore [72].
Facile fabrication of a second-order nonlinear optical films with superior properties and stability was reported [73] using a surface sol-gel synthesis of ZrO2 layers and subsequent layer-by-layer (LbL) deposition of the nonlinear optical (NLO)-active azobenzene-containing polyanion and poly(diallyldimethylammonium chloride). The resulted material is an organic/inorganic hybrid multilayer film with noncentrosymmetrically orientated azobenzene chromophores. The specific orientation of the NLO-active azobenzene chromophores is produced by the strong repulsive interactions between the negatively charged ZrO2 and the sulfonate groups of the sulfonate-modified azobenzene chromophore.
The SHG signal could be increased by increasing the number of deposition cycles and also with the increase of the azobenzene graft ratio in the polyion. Wang et al. [74] proposed a method to fabricate an organic/inorganic hybrid NLO film by electric field-induced layer-by-layer deposition technique. The compound used to produce alternative layers is a new synthesized polycation from aromatic diazo group linked silicon and a chromophore molecule 2-({4-[4-(2-carboxy-2-cyano-vinyl)-phenylazo]-phenyl}-methyl-amino)-ethyl acid (DRCB) as anion.
Using electric field in assembling process, the oriented adsorption of chromophores is facilitated, and the density of oriented optic active molecules increases. The preparation of the hybrid film using LbL deposition of aromatic diazonium salt-linked silicon sol (ADS) and DRCB chromophore on ITO glass previously functionalized with (3-mercaptopropyl)-trimethoxysilane (MTPS) is presented in Figure 13.
The UV irradiation of deposited multilayered films results in transformation of the electrostatic interaction between layers in covalent bonds, leading to a significant increase of the thermal and chemical stability of the final material. The architecture assembles with the aid of the electric field ensuring a high degree of molecular orientation of chromophores; thus, large second-harmonic generation signal of the LbL film was observed.
5. Theoretical modeling
In order to rational design the host-guest material, molecular dynamic simulation is used for quantum chemical calculation. The structures of considered molecules are simulated by using molecular dynamics, and relevant electrical properties, such as polarizability α and β, could be computed with density functional theory (DFT). For example, Makowska-Janusik (3) reports the investigation of the influence of polymeric matrix on the NLO properties of the pyrazoloquinoline derivatives in poly(methyl methacrylate) matrix. According to the chemical structure of the chromophore molecules, the best description of the pyrazoloquinolines-PMMA systems could be obtained by using various approaches, such as point-dipole or distributed molecular response models, with good concordance with the experimental data. Molecular simulation is also performed in order to elucidate the origin of the NLO behavior in composite materials, since in experimental approach it is not possible to separate the contributions of each component. The molecular modeling methods can provide explanations about the nature of the guest-host interaction based on the separate different contribution of the components to the optical properties.
A particular kind of host-guest material exhibiting NLO properties is obtained by using semiconducting nanoparticles (quantum dots) as optical active materials. The interface phenomena play an important role in tuning the NLO properties of these materials.
An innovative approach is reported by Britton et al. [75], to significantly increase the nonlinear properties when combining in the polymeric matrix a low symmetry phthalocyanine derivative with CdSe/CdS quantum dots. The new synthesized metal-free chromophore 2,3-bis[2′-(2″-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-
6. Conclusion
The synthesis of the most important classes of the organic compounds, alkyne, dye, heterocycle, thienyl, and ferrocene compounds, was presented. A lot of important reactions, like Sonogashira, Suzuki, Heck, Huisgen, Wadsworth-Emmons, Vilsmeier-Haack-Arnold, Wittig, etc., were employed for the synthesis of the new compounds with nonlinear optical applications. The synthesis of the new molecules possessing privileged structures, with a couple donor-acceptor or “push-pull” molecules, was the purpose of the last decades. Besides, new unorthodox structures, which do not possess this system, but with very good NLO properties and very good SHG signal, were reported, and the number of these increase every year. The most important parameters in the characterization of the new NLO organic compounds are the HOMO-LUMO energy gap and the first-order hyperpolarizability βtot. Small energy gaps and high hyperpolarizabilities define the best compounds with nonlinear optical applications.
Thin films were fabricated by incorporating substances with NLO properties in a large variety of polymers to improve the performance of the resulted hybrid system. Polymethyl methacrylate is the most used polymer, but silica matrix is preferred. Also, Disperse Red 1 in a silica glass allows uniform dispersion and arrangement of the chromophore molecules in the cross-linked polymeric matrix. The new hybrid films are fabricated by sol-gel synthesis. The morphology of the silica matrix is very important for a good NLO behavior. Each class of organic compounds possesses a specific method for the fabrication of the thin films in order to increase their NLO properties. Thus, azo-photosensitives dyes are encapsulated. Noncentrosymmetric arrangement for the dipolar push-pull chromophores embedded in a polymeric matrix is obtained when heating the system to the glass transition temperature (T)g of the polymer. Langmuir-Blodgett films, which exhibit better NLO properties, are obtained from Langmuir film deposited at the air-water interfaces with the well-known orientation of the molecule with the hydrophobic groups in air and hydrophilic ones immersed in water. A convenient technique for the fabrication of thin films is the layer-by-layer (LbL) method which presents the advantage of the precise control of the composition and thickness of the final film. Both theoretical modeling and experimental approach should be addressed, in order to find the best matching between the host and guest material. In addition, the influence of the surface and film formation method should be considered, with a particular attention to the thermo- or photosensitive chromophores.
List of abbreviations
SHG | Second-harmonic generation |
HOMO-LUMO gap | The difference between the energy of the highest occupied molecular orbital and the lowest unoccupied molecular orbital (eV) |
α | Molecular polarizability (esu·D) |
βtot | First-order hyperpolarizability (esu·D) |
μtot | Dipole moment (D) |
Q | Quadrupole moment (D) |
Tg | Glass transition temperature (°C) |
LbL | Layer-by-layer deposition technique |
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